CN112608261A - Method for preparing methionine - Google Patents
Method for preparing methionine Download PDFInfo
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- CN112608261A CN112608261A CN202011491170.6A CN202011491170A CN112608261A CN 112608261 A CN112608261 A CN 112608261A CN 202011491170 A CN202011491170 A CN 202011491170A CN 112608261 A CN112608261 A CN 112608261A
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- aminobutyronitrile
- methionine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/06—Preparation of carboxylic acid amides from nitriles by transformation of cyano groups into carboxamide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention aims at the technical field of methionine preparation, and particularly relates to a method for preparing methionine; under the action of cerium oxide catalyst, the concentration of inorganic acid radical in ammoniated liquid containing aminobutyronitrile is controlled, aminobutyronitrile solution containing ammonia with certain concentration is catalyzed and hydrolyzed, aminobutyrylamide intermediate product is hydrolyzed into hydrolysate containing 2-amino-4-methylthio ammonium butyrate, and the hydrolysate is deaminated, decolored, crystallized and separated to obtain methionine product. The invention can effectively improve the activity and the service life of the solid catalyst by controlling the concentration of inorganic acid radical ions in the ammoniation liquid; in addition, the cerium oxide catalyst is recycled after solid-liquid separation and washing regeneration by a solvent.
Description
Technical Field
The invention aims at the technical field of methionine preparation, and particularly relates to a method for preparing methionine.
Background
D, L-methionine, as amino acid feed additive in feed, is an animal growth promoter, is used for protein synthesis, and can improve feed conversion rate, animal growth rate and poultry egg laying rate. It can promote the growth of fowl and livestock, increase lean meat amount, shorten breeding period, and save about 40% of feed by adding methionine into animal feed.
At present, the production method of D, L-methionine mainly comprises a chemical synthesis method, a biological fermentation method and an enzyme catalysis method, wherein the chemical synthesis method is the most common method. Two chemical synthesis methods are known. The first one is obtained through direct synthesis of 5- (beta-methylmercapto ethyl) hydantoin (hydantoin) with cyanide, methylmercapto propionaldehyde and ammonium carbonate or other material and alkaline hydrolysis and acidification, or through first preparation of 2-hydroxy-4-methylmercapto butyronitrile (cyanohydrin) with hydrogen cyanide and methylmercapto propionaldehyde and synthesis of hydantoin with ammonium carbonate and alkaline hydrolysis and acidification. When the D, L-methionine is obtained by the method through hydantoin alkaline hydrolysis and acidification, a large amount of alkali is consumed, a large amount of inorganic salt with low additional value is generated, the feed liquid circulation amount is large, and the energy consumption is high. The second method is that 2-amino-4-methylthiobutyronitrile (called 'aminobutyronitrile' for short) is catalyzed and hydrolyzed to prepare 2-amino-4-methylthiobutanamide (called 'aminobutyronitrile' for short), and then the D, L-methionine is prepared through further hydrolysis. Because alpha positions of the cyanohydrin and the aminobutyronitrile have amino or hydroxyl which are electron-withdrawing groups, the influence on adjacent nitrile groups is large, and the conventional catalyst is obviously different from other nitrile compounds in properties, so that the hydrolysis of the aminobutyronitrile is difficult to catalyze by the conventional catalyst.
Chinese patent CN1211360C discloses a method for preparing D, L-methionine, which comprises the following steps: hydrolyzing methionine aminonitrile in the presence of ketone catalyst and hydroxide basic resin to obtain methionine aminoamide, hydrolyzing methionine aminoamide to obtain ammonium methionine through ammonia hydrolyzing catalyst or oxide catalyzed hydrolysis or enzyme catalyzed hydrolysis, and eliminating ammonia to obtain D, L-methionine. The method has low yield, the yield of the first step hydrolysis is only 82.3%, the catalyst ketone and the reaction materials are mutually soluble, the problem of difficult separation and recovery of the catalyst exists, and the hydroxyl ion exchange resin needs to be added with alkali for regeneration to form salt; the second step chemical method has poor catalytic effect, the catalytic hydrolysis yield is only 85 percent, and the whole process is not suitable for industrial production.
Chinese patent CN16718557A discloses a method for preparing methionine, which uses a biocatalyst with hydrolytic activity to hydrolyze 2-amino-4-methylthiobutyronitrile to obtain methionine, the selected biocatalyst is immobilized bacteria, the method has the problems of biocatalyst selection, low hydrolysis yield, and the whole process is not suitable for industrial production.
Chinese patent CN107108487A discloses a method for preparing methionine by hydrolyzing 2-amino-4- (methylthio) butyronitrile in one step by adopting a one-pot method in the presence of a cerium oxide catalyst; the method has the problems that nitrile polymerization is generated in the hydrolysis process, colored substances are formed, the color of hydrolysate is dark, the product quality is influenced (the color of the product is yellow), meanwhile, the hydrolysis is not thorough, the yield is low, the hydrolysis time is long, and the service life of the catalyst is short.
Chinese patent CN1400966A discloses a method for preparing D, L-methionine, which comprises the following steps: 2-hydroxy-4-methylthiobutyronitrile is contacted with pure ammonia to prepare 2-amino-4-methylthiobutyronitrile, after the reaction is finished, excess ammonia is removed, then aminobutyrylamide is prepared by hydrolysis in the presence of ketone and metal alkali hydroxide, all unreacted ketone, ammonia and water are removed, the methionine amide is hydrolyzed in the presence of a catalyst containing titanium to obtain ammonium methionine, and methionine is released from the ammonium methionine salt. The method adopts ketone as a catalyst, and the catalyst is difficult to separate and recover because the catalyst and reaction materials are mutually soluble; metal alkali hydroxides lead to final acidification to form salts; in addition, the ammoniated liquid containing the aminobutyronitrile has more inorganic acid radical ions, damages the subsequent catalyst adopting the metal alkali hydroxide, influences the activity of the catalyst adopting the metal alkali hydroxide, has low yield of the methionine, and is not suitable for industrial production.
Chinese patent CN1103066A discloses a continuous production method of methionine or methionine derivatives, which specifically comprises: a process for producing methionine or a methionine salt by hydrolysis of methionine nitrile to methionine amide in the presence of a ketone followed by saponification with alkali, ammonia, ketone and water being removed together during and/or after saponification of the amide at a temperature of 85 ℃ or more and/or by vacuum; among them, hydrolysis with a base is disclosed, but hydrolysis using a solid base catalyst is not mentioned.
In summary, the current preparation process of D, L-methionine has the main problems: (1) a large amount of alkali is consumed, and a large amount of inorganic salt with low added value is produced as a byproduct; (2) the catalyst is quick in inactivation, is not recycled and regenerated, is not used for subsequent production, has less cycle times, high process cost and low yield, and is not suitable for industrial production; (3) nitrile polymerization is generated in the hydrolysis process, and colored substances are formed to cause the color of hydrolysate to be dark, so that the product quality is influenced; (4) the ammoniated liquid containing the aminobutyronitrile has more inorganic acid radical ions, can damage subsequent catalysts adopting metal alkali hydroxides, influences the activity of the catalysts adopting the metal alkali hydroxides, has low yield of the methionine, and is not suitable for industrial production; (5) cyanohydrins are unstable and require storage under acidic conditions, and can introduce inorganic acids that affect the activity of the metal alkali hydroxide catalyst.
To this end, a process for producing methionine is proposed.
Disclosure of Invention
The invention aims to provide a method for preparing methionine, which controls the concentration of inorganic acid radicals in ammoniated liquid containing aminobutyronitrile before the first hydrolysis, and does not damage a solid catalyst and influence the activity of the solid catalyst when the ammoniated liquid containing aminobutyronitrile is hydrolyzed under the condition of the solid catalyst, so that the service life of the solid catalyst is long; the solid catalyst can be recycled and regenerated, and the subsequent production can be applied mechanically, so that the raw material cost and the energy consumption can be effectively reduced, and the method is suitable for industrial production.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a process for preparing methionine includes such steps as catalytic hydrolysis of aminobutyronitrile solution containing ammonia in a certain concentration under the action of cerium oxide catalyst, hydrolyzing the aminobutyronitrile solution to obtain the hydrolyzed liquid containing 2-amino-4-methylthio ammonium butyrate, deaminizing, decolouring, crystallizing and separating to obtain methionine product, and washing cerium oxide catalyst and said hydrolyzed liquid with solvent for reuse.
Specifically, the concentration of inorganic acid radical ions in the aminobutyronitrile solution needs to be controlled, and if the concentration of inorganic acid radical ions in the aminobutyronitrile solution is not controlled, the solid catalyst doped in the subsequent hydrolysis reaction is damaged, so that the activity and the service life of the solid catalyst are influenced.
In order to further reduce the influence of a large amount of inorganic acid radical ions on the solid catalyst and reduce the cost and the energy consumption of the solid catalyst, the concentration of the inorganic acid radical in the amino butyronitrile-containing ammoniated liquid is controlled to be less than 0.1 percent before the first hydrolysis, so that the content of the inorganic acid radical ions in the amino butyronitrile-containing ammoniated liquid can be effectively controlled, the solid catalyst cannot be damaged when the amino butyronitrile-containing ammoniated liquid is hydrolyzed under the condition of the solid catalyst, the activity of the solid catalyst cannot be influenced, and the service life of the solid catalyst is long.
In order to further reduce the polymerization of nitrile in the hydrolysis process to improve the quality of the product, in the method, the mass fraction of ammonia in the ammoniated liquid containing the aminobutyronitrile needs to be controlled to be 1-8%.
In order to further reduce the polymerization of nitrile in the hydrolysis process so as to improve the quality of products, in the method, the mass ratio of the cerium oxide catalyst to the ammoniated liquid containing aminobutyronitrile is 0.1-0.5: 1.
in order to further reduce the polymerization of nitrile in the hydrolysis process so as to improve the quality of the product, in the method, the hydrolysis temperatures of two steps are 50-70 ℃ and 70-110 ℃ respectively, and the hydrolysis pressure of the two steps is normal pressure or not higher than 0.2 MPa.
In order to further reduce the cost and energy consumption of the solid catalyst and be suitable for industrial production, in the method, after the first hydrolysis reaction is finished, the hydrolysate is filtered, the solid catalyst is recovered, and the solid catalyst is washed by water, so that the regeneration of the solid catalyst can be realized.
Specifically, the method for preparing methionine comprises the following steps:
(1) controlling the concentration of inorganic acid radicals in the amino butyronitrile-containing ammoniated liquid: controlling the concentration of inorganic acid radicals in the ammoniated liquid containing the aminobutyronitrile to be less than 0.1 percent;
(2) first hydrolysis reaction: adding the adjusted ammoniated liquid containing the aminobutyronitrile and a solid catalyst into a reaction device, hydrolyzing at the temperature of 55-70 ℃ and under the normal pressure or not higher than 0.2MPa, reacting to generate aminobutanamide, and judging the reaction end point by a central control system;
(3) and (3) second hydrolysis reaction: controlling the temperature at 70-110 ℃, hydrolyzing under normal pressure or not higher than 0.2MPa, reacting to generate D, L-methionine, and then performing deamination, decoloration, crystallization and separation to obtain a methionine product;
(4) recovering and regenerating the solid catalyst: carrying out sedimentation separation and filtration on the cerium oxide catalyst and hydrolysate, and then washing and regenerating the cerium oxide catalyst by using a solvent for recycling, wherein the washing solvent is water, alcohol or a mixture thereof;
(5) and (3) recycling: the recovered and regenerated solid catalyst is applied to the first hydrolysis reaction.
Further, the hydrolysis reaction involved in the invention is as follows:
the invention has the beneficial effects that:
(1) the invention provides a method for preparing methionine, wherein before hydrolysis, the concentration of inorganic acid radicals in ammoniated liquid containing aminobutyronitrile is controlled, so that the solid catalyst is not damaged and the activity of the solid catalyst is not influenced when the subsequent hydrolysis reaction is carried out under the condition of the solid catalyst, meanwhile, the activity of the solid catalyst is high, and the yield of the methionine product is high;
(2) the invention provides a method for preparing methionine, which can realize the recovery and regeneration of a solid catalyst by carrying out deamination, decoloration, crystallization and separation on hydrolysate and can effectively reduce the cost and energy consumption of raw materials when the solid catalyst is used for subsequent production, the solid catalyst has long service life, the activity of the regenerated solid catalyst is high, the yield of the methionine product is maintained above 96% after the solid catalyst is reused for 20 times, and the economic benefit is obviously improved compared with the prior art;
(3) the invention provides a method for preparing methionine, which is simple and suitable for industrial production.
Detailed Description
The present invention is described in detail below with reference to specific examples, which are given for the purpose of further illustrating the invention and are not to be construed as limiting the scope of the invention, and the invention may be modified and adapted by those skilled in the art in light of the above disclosure. Except for special description, the parts are parts by weight, the percentages are mass percentages, and the concentration is mass percentage concentration.
Example 1 (cerium oxide as catalyst, batch 1)
Under the action of a cerium oxide catalyst, controlling the concentration of inorganic acid radicals in ammoniated liquid containing aminobutyronitrile to be 0.09%, wherein aminobutyronitrile solution containing ammonia with certain concentration is subjected to catalytic hydrolysis, and is hydrolyzed into hydrolysate containing 2-amino-4-methylthio ammonium butyrate through an aminobutyrylamide intermediate product, wherein the mass ratio of the cerium oxide catalyst to the ammoniated liquid containing aminobutyronitrile is 0.5: 1, ammonia mass percent of ammoniated liquid containing the aminobutyronitrile is 8 percent, and then deamination, decoloration, crystallization and separation are carried out to obtain the methionine product.
Specifically, the cerium oxide catalyst and the hydrolysate are subjected to sedimentation separation and filtration, and then the cerium oxide catalyst is washed by a solvent and regenerated for recycling, wherein the washing solvent is water.
Specifically, the two-step hydrolysis temperature is 50-70 ℃ and 70-110 ℃, and the two-step hydrolysis pressure is normal pressure.
Example 2 (cerium oxide as catalyst)
Under the action of a cerium oxide catalyst, controlling the concentration of inorganic acid radicals in ammoniated liquid containing aminobutyronitrile to be 0.05%, wherein aminobutyronitrile solution containing ammonia with certain concentration is subjected to catalytic hydrolysis, and is hydrolyzed into hydrolysate containing 2-amino-4-methylthio ammonium butyrate through an aminobutyrylamide intermediate product, wherein the mass ratio of the cerium oxide catalyst to the ammoniated liquid containing aminobutyronitrile is 0.3: 1, the mass fraction of ammonia in ammoniated liquid containing the aminobutyronitrile is 6 percent, and then the ammoniation, the decoloration, the crystallization and the separation are carried out to obtain the methionine product.
Specifically, the cerium oxide catalyst and the hydrolysate are subjected to sedimentation separation and filtration, and then the cerium oxide catalyst is washed by a solvent and regenerated for recycling, wherein the washing solvent is water.
Specifically, the two-step hydrolysis temperature is 50-70 ℃ and 70-110 ℃, and the two-step hydrolysis pressure is 0.2 MPa.
Example 3 (cerium oxide as catalyst)
Under the action of a cerium oxide catalyst, controlling the concentration of inorganic acid radicals in ammoniated liquid containing aminobutyronitrile to be 0, wherein aminobutyronitrile solution containing ammonia with certain concentration is subjected to catalytic hydrolysis, and is hydrolyzed into hydrolysate containing 2-amino-4-methylthio ammonium butyrate through an aminobutyrylamide intermediate product, wherein the mass ratio of the cerium oxide catalyst to the ammoniated liquid containing aminobutyronitrile is 0.1: 1, ammonia mass percent of ammoniated liquid containing the aminobutyronitrile is 1 percent, and then the ammoniated liquid is subjected to deammoniation, decoloration, crystallization and separation to obtain a methionine product.
Specifically, the cerium oxide catalyst and the hydrolysate are subjected to sedimentation separation and filtration, and then the cerium oxide catalyst is washed by a solvent and regenerated for recycling, wherein the washing solvent is water.
Specifically, the two-step hydrolysis temperature is 50-70 ℃ and 70-110 ℃, and the two-step hydrolysis pressure is 0.2 MPa.
Application test examples
Example 4 (cerium oxide as catalyst, catalyst application 1 st batch)
Under the action of applying batch 1 of cerium oxide catalyst, the concentration of inorganic acid radicals in ammoniated liquid containing aminobutyronitrile is controlled to be 0.09%, wherein aminobutyronitrile solution containing ammonia with certain concentration is subjected to catalytic hydrolysis, and is hydrolyzed into hydrolysate containing 2-amino-4-methylthio ammonium butyrate through aminobutyrylamide intermediate product, wherein the mass ratio of the cerium oxide catalyst to the ammoniated liquid containing aminobutyronitrile is 0.5: 1, ammonia mass percent of ammoniated liquid containing the aminobutyronitrile is 8 percent, and then deamination, decoloration, crystallization and separation are carried out to obtain the methionine product.
Example 5 (cerium oxide as catalyst, catalyst application 2)
Under the action of applying batch 2 of cerium oxide catalyst, the concentration of inorganic acid radicals in ammoniated liquid containing aminobutyronitrile is controlled to be 0.09%, wherein aminobutyronitrile solution containing ammonia with certain concentration is subjected to catalytic hydrolysis, and is hydrolyzed into hydrolysate containing 2-amino-4-methylthio ammonium butyrate through aminobutyrylamide intermediate product, wherein the mass ratio of the cerium oxide catalyst to the ammoniated liquid containing aminobutyronitrile is 0.5: 1, ammonia mass percent of ammoniated liquid containing the aminobutyronitrile is 8 percent, and then deamination, decoloration, crystallization and separation are carried out to obtain the methionine product.
Example 6 (cerium oxide as catalyst, catalyst application No. 3 to 19)
Under the action of applying batch 3 of cerium oxide catalyst, the concentration of inorganic acid radicals in ammoniated liquid containing aminobutyronitrile is controlled to be 0.09%, wherein aminobutyronitrile solution containing ammonia with certain concentration is subjected to catalytic hydrolysis, and is hydrolyzed into hydrolysate containing 2-amino-4-methylthio ammonium butyrate through aminobutyrylamide intermediate product, wherein the mass ratio of the cerium oxide catalyst to the ammoniated liquid containing aminobutyronitrile is 0.5: 1, ammonia mass percent of ammoniated liquid containing the aminobutyronitrile is 8 percent, and then deamination, decoloration, crystallization and separation are carried out to obtain the methionine product.
Referring to the method, the 4 th to 19 th batch circulation production is carried out.
Example 7 (cerium oxide as catalyst, catalyst application No. 20)
Under the action of applying a 19 th batch of cerium oxide catalyst, controlling the concentration of inorganic acid radicals in the ammoniated liquid containing aminobutyronitrile to be 0.09%, wherein the aminobutyronitrile solution containing ammonia with certain concentration is subjected to catalytic hydrolysis, and is hydrolyzed into hydrolysate containing 2-amino-4-methylthio ammonium butyrate through an aminobutyrylamide intermediate product, wherein the mass ratio of the cerium oxide catalyst to the ammoniated liquid containing aminobutyronitrile is 0.5: 1, ammonia mass percent of ammoniated liquid containing the aminobutyronitrile is 8 percent, and then deamination, decoloration, crystallization and separation are carried out to obtain the methionine product.
Comparative example 1
The difference between the comparative example and the example 1 is that the concentration of the inorganic acid radical in the ammoniated liquid containing the aminobutyronitrile is controlled to be 0.1 percent before the first hydrolysis.
Comparative example 2
The difference between the comparative example and the example 1 is that the concentration of inorganic acid radical in the ammoniated liquid containing aminobutyronitrile is controlled to be 1 percent before the first hydrolysis.
COMPARATIVE EXAMPLE 3 (COMPARATIVE BATCH 1)
The difference between the comparative example and the example 1 is that the mass fraction of ammonia in the ammoniated liquid containing the aminobutyronitrile in the comparative example is 0.5%, after the hydrolysis reaction is finished, the mixture is filtered, the solid catalyst is recovered, and the solid catalyst is directly applied to the next hydrolysis reaction without being washed by water.
Comparative example 4 (catalyst application comparative example 3 for comparative application 1 st batch)
The difference between the comparative example and the example 1 is that the ammoniated solution containing the aminobutyronitrile in the comparative example reacts with the solid catalyst in the comparative example 3 (batch 1 for comparison), wherein the mass fraction of ammonia in the ammoniated solution containing the aminobutyronitrile is 9%.
Comparative example 5 (comparative example 4 for catalyst application and comparative example 2)
The difference between the comparative example and the example 1 is that the ammoniated solution containing the aminobutyronitrile in the comparative example reacts with the solid catalyst in the indiscriminate comparative example 4 (batch 1), wherein the mass fraction of ammonia in the ammoniated solution containing the aminobutyronitrile is 9%.
Comparative example 6 (comparative example 5 for catalyst application, 3 rd to 19 th batch for comparison)
The ammonification liquid containing the aminobutyronitrile in the comparative example reacts with the solid catalyst in the comparative example 5 (comparative example 1), wherein the mass fraction of ammonia in the ammonification liquid containing the aminobutyronitrile is 9%.
Referring to the method, the 4 th to 19 th batch circulation production is carried out.
Comparative example 7 (comparative example 6 for catalyst application, 20 th batch for comparison)
The difference between this comparative example and example 1 is that the ammoniated solution containing aminobutyronitrile in this comparative example reacts with the solid catalyst of comparative example 6 (comparative example 19), wherein the mass fraction of ammonia in the ammoniated solution containing aminobutyronitrile is 9%.
Comparative example 8 (comparative example 3 for catalyst application and 1 st batch for comparison)
The difference between the comparative example and the example 1 is that the aminobutyronitrile-containing ammoniated liquid in the comparative example reacts with the solid catalyst in the comparative example 3 (batch 1 is used for comparison) in a indiscriminate way, the concentration of inorganic acid radicals in the aminobutyronitrile-containing ammoniated liquid is controlled to be 0.1%, and the mass fraction of ammonia in the aminobutyronitrile-containing ammoniated liquid is controlled to be 0.5%.
Comparative example 9 (comparative example 3 for catalyst application and 1 st batch for comparison)
The difference between the comparative example and the example 1 is that the aminobutyronitrile-containing ammoniated liquid in the comparative example reacts with the solid catalyst in the comparative example 3 (batch 1 is used for comparison) in a way that the concentration of inorganic acid radicals in the aminobutyronitrile-containing ammoniated liquid is controlled to be 1 percent, and the mass fraction of ammonia in the aminobutyronitrile-containing ammoniated liquid is controlled to be 9 percent.
The methionine content was detected by a liquid phase method, and the yield of the hydrolysis reaction was calculated, and the analysis data of the results of examples 1 to 7 of the present invention and comparative examples 1 to 9 are shown in table 1.
TABLE 1 data for examples 1-7 and comparative examples 1-9
According to the invention, the concentration of inorganic acid radicals in the ammoniated liquid containing the amino butyronitrile is controlled before the first hydrolysis, so that the solid catalyst is not damaged and the activity of the solid catalyst is not influenced when the ammoniated liquid containing the amino butyronitrile is hydrolyzed under the condition of the solid catalyst; after the first hydrolysis reaction is finished, the solid catalyst is filtered and recovered, and is washed by water, so that the recovery and regeneration of the solid catalyst can be realized, the solid catalyst can be used for subsequent production, the raw material cost and the energy consumption can be effectively reduced, the service life of the solid catalyst is long, the activity of the regenerated solid catalyst is high, the yield of the methionine product is maintained to be more than 96% after the solid catalyst is reused for 20 times, the economic benefit is obviously improved compared with the prior art, and the method is suitable for industrial production.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (5)
1. A method for preparing methionine is characterized in that under the action of a cerium oxide catalyst, the concentration of inorganic acid radicals in ammoniation liquid containing aminobutyronitrile is controlled, aminobutyronitrile solution containing ammonia with a certain concentration is subjected to catalytic hydrolysis, an aminobutyronitrile intermediate product is hydrolyzed into hydrolysate containing 2-amino-4-methylthio ammonium butyrate, the hydrolysate is subjected to deamination, decoloration, crystallization and separation to obtain a methionine product, and the cerium oxide catalyst and the hydrolysate are subjected to solid-liquid separation and are washed and regenerated by a solvent and then are recycled.
2. The method for preparing methionine according to claim 1, wherein the mass fraction of ammonia in the ammoniated solution containing aminobutyronitrile is 1-8%.
3. The method for preparing methionine as claimed in claim 1, wherein the concentration of inorganic acid radical in the amino butyronitrile-containing ammoniated liquid is controlled to be less than 0.1%.
4. The method for preparing methionine as claimed in claim 1, wherein the cerium oxide catalyst is separated from the hydrolysate by settling and filtering, and the cerium oxide catalyst is washed with a solvent, such as water, alcohol or a mixture thereof, and then regenerated for recycling.
5. The method for preparing methionine according to claim 1, wherein the mass ratio of the cerium oxide catalyst to the amino-butyronitrile-containing ammoniated liquid is 0.1-0.5: 1, the hydrolysis temperatures of the two steps are 50-70 ℃ and 70-110 ℃, respectively, and the hydrolysis pressure of the two steps is normal pressure or not higher than 0.2 MPa.
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| CN113416159A (en) * | 2021-04-21 | 2021-09-21 | 重庆紫光化工股份有限公司 | Method for preparing DL-methionine by decoloring and crystallizing methionine ammonium salt |
| CN114213293A (en) * | 2021-12-23 | 2022-03-22 | 天宝动物营养科技股份有限公司 | Preparation method of methionine |
| CN114507150A (en) * | 2022-02-22 | 2022-05-17 | 天宝动物营养科技股份有限公司 | Hydantoin precursor liquid and method for preparing glycine by using hydantoin precursor liquid |
| WO2023144265A1 (en) | 2022-01-28 | 2023-08-03 | Evonik Operations Gmbh | Granular catalyst for the hydrolysis of amino nitriles and amino amides to amino acids or derivatives thereof |
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| WO2023144265A1 (en) | 2022-01-28 | 2023-08-03 | Evonik Operations Gmbh | Granular catalyst for the hydrolysis of amino nitriles and amino amides to amino acids or derivatives thereof |
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